Black photoresist composition as well as preparation method and application thereof

Abstract

The invention relates to a black photoresist composition which comprises (A) 3.00-6.00 parts by weight of photosensitive epoxy acrylic resin, (B) 10-15 parts by weight of a black pigment enhancer, (C) 10-25 parts by weight of an active diluent containing acrylate groups and unsaturated double bonds, (D) 1-6 parts by weight of a photoinitiator and (E) 0.5-5 parts by weight of an auxiliary agent, (F) 50-70 parts by weight of a solvent, and the amount of each component is based on 100 parts by weight of the total weight of the composition; the invention also relates to a preparation method of the composition. The invention also discloses a black frame prepared from the composition and application of the black frame to preparation of a touch screen, a light splitting recognizer device and an automobile welcome lamp device.

Description

Technical Field

[0001] The present invention relates to a photoresist composition, and more specifically, to a black photoresist composition, a preparation method thereof, and use thereof in preparing a touch screen, especially a vehicle-mounted touch screen, and in preparing a spectroscopic identifier device and a vehicle welcome light device. Background Art

[0002] With the development of Internet of Things technology, higher requirements are put forward for black photoresist for touch panel (TP), especially for black photoresist used in advanced processes such as OGS (On-Glass Sensor, where the touch sensor is directly etched on the glass substrate of the display panel) and OGM (On-Glass Model, where an independent touch sensor glass is used and manufactured separately from the display panel). OGS and OGM processes usually need to be carried out in more severe environments, such as high-intensity ultraviolet light irradiation and extreme chemical corrosion, which requires the photoresist to not only maintain good photosensitivity and resolution, but also have excellent UV resistance and strong acid and alkali resistance.

[0003] In particular, for the automotive industry, due to the complex and changeable environment in which automobiles are located, and the precision components of advanced driver assistance systems (ADAS) sensors in the automotive field also put forward higher requirements for the recognition and analysis of light, there are more stringent standards for the physical properties of photoresists such as temperature resistance range, resistance to ultraviolet aging, and mechanical strength.

[0004] However, the existing black photoresist for TP has low reliability in high temperature and high humidity environments. Long-term exposure to such environments may cause material performance degradation, thereby affecting the function of the entire touch panel. Secondly, the existing black photoresist for TP has poor resistance to strong acid etching, and ordinary black photoresist for TP is easily degraded under ultraviolet light, which means that the product life will be greatly shortened when used outdoors or exposed to sunlight for a long time.

[0005] As we all know, TP photoresist is mainly used in the field of touch screens, among which TP BM (Black Matrix) belongs to the first photoresist process. On the glass side, it will be directly exposed to sunlight and affected by various physical or chemical aspects of life. On the other side, the subsequent preparation process will go through a variety of metal coating processes, which will involve exposure to harsh chemical environments such as high temperature and strong acids and alkalis. The BM used in TFT-LCD has more stringent requirements on display effects such as line fineness and linearity.

[0006] Therefore, it is necessary to provide a black photoresist that is resistant to high temperature and humidity, strong acid etching, and ultraviolet light. Summary of the invention

[0007] The object of the present invention is achieved by providing a black photoresist composition, which comprises:

[0008] (A) photosensitive epoxy acrylic resin, 3.00-6.00 parts by weight, preferably 4.02-5.70 parts by weight, more preferably 5.03-5.70 parts by weight;

[0009] (B) pigment, 10-15 parts by weight, preferably 11.65-13.5 parts by weight, more preferably 12.36-13.06 parts by weight;

[0010] (C) a reactive diluent containing an acrylate group and an unsaturated double bond, 10-25 parts by weight, preferably 18-21 parts by weight;

[0011] (D) photoinitiator, 1-6 parts by weight, preferably 2-5 parts by weight;

[0012] (E) auxiliary agent, 0.5-5 parts by weight;

[0013] (F) solvent, 50-70 parts by weight, preferably 50-60 parts by weight, more preferably 53-59 parts by weight;

[0014] The amounts of components (A) to (F) are based on 100 parts by weight of the total weight of the photoresist composition.

[0015] The photosensitive epoxy acrylic resin has a number average molecular weight of 5000-15000 g / mol, preferably 8000-14000 g / mol, more preferably 8500-9500 g / mol, an epoxy value of 0.003-0.30 mol / 100 g, preferably 0.15-0.25 mol / 100 g, more preferably 0.18-0.22 mol / 100 g, and an acid value of 70-120 mg KOH / g, preferably 85-95 mg KOH / g.

[0016] In one aspect, the present invention also provides a method for preparing the above-mentioned black photoresist composition, comprising the following steps:

[0017] I) preparing photosensitive epoxy acrylic resin, comprising the following steps:

[0018] An acrylic acid ester and an acid anhydride containing an unsaturated double bond are added into a reaction vessel as an initial mixture in a weight ratio of 5:1 to 1:1, preferably 1.7:1 to 1.1:1, wherein the initial acid value of the initial mixture is 250-350 mg KOH / g, and prepolymerization is performed, wherein the reaction temperature is 80-100° C., preferably 85-95° C., to form a prepolymer,

[0019] (2) when the acid value of the prepolymer is reduced to half of the initial acid value, epoxy resin is immediately added to the prepolymer and reacted at the temperature in step (1) for 1-2 hours, preferably 1.3-1.7 hours,

[0020] (3) raising the temperature of the reaction mixture to 100-130° C. and maintaining the elevated reaction temperature until the acid value decreases to 90-110 mg KOH / g,

[0021] (4) adding a free radical polymerization initiator to continue the reaction until the acid value drops to 70-90 mg KOH / g, stopping heating, and allowing the mixture to cool naturally to room temperature, thereby obtaining a photosensitive epoxy acrylic resin.

[0022] ii) mixing the photosensitive epoxy acrylic resin obtained in step i) with a black pigment enhancer (B), a reactive diluent containing an acrylate group and an unsaturated double bond (C), a photoinitiator (D), an auxiliary agent (E) and a solvent (F) in the above proportions at room temperature for 1.5-2.5 hours to uniformly mix them, so as to obtain a black photoresist composition.

[0023] On the other hand, the present invention provides a black frame or other pattern, such as formed by coating, pre-baking, exposing, developing and post-baking the above-mentioned black photoresist composition containing photosensitive epoxy acrylic resin.

[0024] In yet another aspect, the present invention provides a black frame used as a frame material for a vehicle-mounted touch screen display.

[0025] In another aspect, the present invention provides a black pattern using the above black photoresist composition as a main material of a spectroscopic identifier.

[0026] The invention provides a black pattern, using the black photoresist composition as the main material of a car welcome lamp.

[0027] The coating of the black photoresist composition provided by the present invention is not easy to fall off and fail under high temperature and high humidity, strong acid and strong alkali, and long-term UV irradiation, showing excellent performance and meeting the application scenarios with high requirements for chemical corrosion resistance and reliability. DETAILED DESCRIPTION

[0028] In the present invention, unless otherwise stated, all operations are carried out at room temperature and normal pressure.

[0029] Before describing the compositions, methods and methodology of the present invention in more detail, it should be understood that the present disclosure is not limited to the specific compositions, methods and experimental conditions described, because such compositions, methods and conditions may vary. It should also be understood that the terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention.

[0030] In the present invention, the acid value refers to the value obtained by the acid-base titration method with the aid of a KOH standard solution according to GB / T2895-2008. The viscosity is measured according to the unsaturated polyester resin test method of GB / T 7193-2008 (VT-4, No. 2 rotor, 60 rpm), and the solid content is measured according to the unsaturated polyester resin test method of GB / T7193-2008. The number average molecular weight is measured by gel permeation chromatography (GPC) according to GB / T 21863-2008 "Gel Permeation Chromatography (GPC) Using Tetrahydrofuran as Eluent" (equivalent to the German standard DIN 55672-1:2007 "Gel Permeation Chromatography (GPC) Part 1: Using Tetrahydrofuran (THF) as Elution Solvent").

[0031] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0032] In the present invention, for example, only the components without solvent are usually considered when calculating material ratios, determining acid values, etc., which is well known to those skilled in the art.

[0033] In the present invention, the terms "black photoresist", "black photoresist composition" and "photosensitive resin composition" are used synonymously.

[0034] In the present invention, the terms "photoinitiator" and "free radical polymerization initiator" are different types of initiators, and the specific types are described in detail below.

[0035] In the present invention, the numerical range involved includes all points within the range and the subsets constituted by them.

[0036] A black photoresist composition comprising the following components:

[0037] (A) photosensitive epoxy acrylic resin, 3.00-6.00 parts by weight, preferably 4.02-5.70 parts by weight, more preferably 5.03-5.70 parts by weight;

[0038] (B) black pigment enhancer, 10-15 parts by weight, preferably 11.65-13.5 parts by weight, more preferably 12.36-13.06 parts by weight;

[0039] (C) a reactive diluent containing an acrylate group and an unsaturated double bond, 10-25 parts by weight, preferably 18-21 parts by weight;

[0040] (D) photoinitiator, 1-6 parts by weight, preferably 2-5 parts by weight;

[0041] (E) auxiliary agent, 0.5-5 parts by weight;

[0042] (F) solvent, 50-70 parts by weight, preferably 50-60 parts by weight, more preferably 53-59 parts by weight;

[0043] The amounts of components (A) to (F) are based on 100 parts by weight of the total weight of the photoresist composition.

[0044] The photosensitive epoxy acrylic resin has a number average molecular weight of 5000-15000 g / mol, preferably 8000-14000 g / mol, more preferably 8500-9500 g / mol, an epoxy value of 0.003-0.30 mol / 100 g, preferably 0.15-0.25 mol / 100 g, more preferably 0.18-0.22 mol / 100 g, and an acid value of 70-120 mg KOH / g, preferably 85-95 mg KOH / g.

[0045] In a preferred embodiment of the present invention, the solid content of the black photoresist composition is 14%-25%.

[0046] In the present invention, in order to achieve better effects, the contents of the components of the photoresist composition of the present invention vary only within a relatively small range.

[0047] (A) Photosensitive epoxy acrylic resin

[0048] In the present invention, the photosensitive epoxy acrylic resin is obtained by reacting an ester of acrylic acid with an acid anhydride containing unsaturated double bonds to form an oligomer, and then reacting with an epoxy resin. The ester of acrylic acid is selected from one or more of methyl methacrylate, β-hydroxypropyl acrylate, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, glycidyl methacrylate (GMA), ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, and lauryl methacrylate. The acid anhydride containing unsaturated double bonds is, for example, maleic anhydride, itaconic anhydride, preferably maleic anhydride. The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, epichlorohydrin, and epoxidized styrene, preferably bisphenol A epoxy resin, wherein bisphenol A epoxy resin is preferably an epoxy resin of model E-51 (purchased from Dow Chemical (Zhangjiagang) Co., Ltd.).

[0049] In a preferred embodiment of the present invention, the photosensitive epoxy acrylic resin is obtained by the following polymerization steps:

[0050] (1) An acrylic acid ester and an acid anhydride containing an unsaturated double bond are added into a reaction vessel as an initial mixture in a weight ratio of 5:1 to 1:1, preferably 1.7:1 to 1.1:1, wherein the initial acid value of the initial mixture is 250-350 mgKOH / g, and prepolymerization is carried out, wherein the reaction temperature is 80-100° C., preferably 85-95° C., to form a prepolymer.

[0051] (2) When the acid value of the prepolymer is reduced to half of the initial acid value, epoxy resin is immediately added to the prepolymer and reacted at the temperature in step (1) for 1-2 hours, preferably 1.3-1.7 hours.

[0052] (3) Raise the temperature of the reaction mixture to 100-130°C and maintain the elevated reaction temperature until the acid value decreases to 90-110 mg KOH / g.

[0053] (4) adding a free radical polymerization initiator to continue the reaction until the acid value drops to 70-90 mg KOH / g, stopping heating, and allowing the mixture to cool naturally to room temperature, thereby obtaining a photosensitive epoxy acrylic resin.

[0054] In the present invention, the free radical initiator used to prepare the photosensitive epoxy acrylic resin is well known to those skilled in the art, including but not limited to: peroxides, such as benzoyl peroxide (BPO), diisopropylbenzene peroxide (DCP), di-tert-butyl peroxide (DTBP); azo compounds, such as azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN).

[0055] In a preferred embodiment of the present invention, in the reaction for preparing the photosensitive epoxy acrylic resin, no free radical initiator is added in the prepolymerization reaction.

[0056] In the present invention, when preparing the photosensitive epoxy acrylic resin, an inhibitor may be added, including but not limited to: phenolic inhibitors, such as hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-p-cresol (BHT), and p-tert-butylcatechol (TBC); quinone inhibitors, such as p-benzoquinone (BQ) and tetrachlorobenzoquinone (TCQ).

[0057] In the present invention, polymerization accelerators may be added when preparing the photosensitive epoxy acrylic resin, including but not limited to: amines, such as N,N-dimethylaniline (DMA), N,N-diethylaniline (DEA), triethylamine (TEA); thiols, such as dodecyl mercaptan (DDM), mercaptoethanol (ME).

[0058] In a preferred embodiment of the present invention, the photosensitive epoxy acrylic resin is prepared by measuring the acid value of the reaction mixture every 0.5-1 hour, and determining the timing of continuing to add materials based on the acid value of the reaction system. That is, the photosensitive epoxy acrylic resin of the present invention is prepared while monitoring the acid value of the polymerization system.

[0059] In a preferred embodiment of the present invention, the preparation reaction of the photosensitive epoxy acrylic resin is carried out under relatively mild conditions to facilitate the determination of the acid value of the reaction mixture during the polymerization process.

[0060] In the comparative example of the present invention, a resin with a cardo structure is used, wherein the cardo structure resin is a type of high-performance polymer with a rigid ring structure, which is connected to the main chain through a "hinge" structure, giving the resin excellent thermal stability, mechanical properties and controllability, and is widely used in the fields of coatings, optical materials, separation membranes, electronic materials, etc. Examples of typical cardo structure resins are polyfluorene ether ketone (PEEK-Cardo) - a fluorene structure is introduced into the main chain of polyether ether ketone (PEEK) to improve its thermal stability and mechanical properties; polyimide (PI-Cardo) - a cardo structure is introduced into the main chain of polyimide for high-performance films and coatings.

[0061] (B) Black Pigment Enhancer

[0062] In the present invention, the black pigment enhancer can be an inorganic or organic pigment, preferably a black pigment enhancer with heat resistance, light resistance and solvent resistance, wherein the black inorganic pigment can be selected from carbon black and titanium black; the black organic pigment can be selected from lactam black and aniline black. In a preferred embodiment of the present invention, the black pigment enhancer can also be selected from Bantian Ink, Sanyang Pigment, Qiangli New Materials, etc.

[0063] In a preferred embodiment of the present invention, the black pigment enhancer is carbon black dispersed in propylene glycol methyl ether acetate, wherein the average particle size of the carbon black is 80-120 nm, preferably 90-110 nm.

[0064] (C) Reactive diluents containing acrylate groups and unsaturated double bonds

[0065] In the present invention, the active diluent containing an acrylate group and an unsaturated double bond (also called a multifunctional active diluent) refers to a compound that can freely copolymerize with an epoxy acrylic resin under the action of a photoinitiator. In the present invention, an active diluent having three or more functional groups is preferred.

[0066] In the present invention, specific examples of the multifunctional reactive diluent include, but are not limited to: pentaerythritol tetraacrylate, pentaerythritol tetraacrylate diglycidyl ether, pentaerythritol tetraacrylate dimethacrylate, pentaerythritol tetraacrylate triglycidyl ether, pentaerythritol tetraacrylate trimethacrylate, pentaerythritol tetraacrylate tetraglycidyl ether, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol tetraacrylate methyl ether , Pentaerythritol tetraacrylate ethyl ether, Pentaerythritol tetraacrylate propyl ether, Pentaerythritol tetraacrylate butyl ether, Pentaerythritol tetraacrylate isobutyl ether, Pentaerythritol tetraacrylate tert-butyl ether, Pentaerythritol tetraacrylate methyl ester, Pentaerythritol tetraacrylate ethyl ester, Pentaerythritol tetraacrylate propyl ester, Pentaerythritol tetraacrylate butyl ester, Pentaerythritol tetraacrylate isobutyl ester, Pentaerythritol tetraacrylate tert-butyl ester, Pentaerythritol tetraacrylate formamide, Pentaerythritol One or more combinations of tetraacrylate acetamide, pentaerythritol tetraacrylate propionamide, pentaerythritol tetraacrylate butyramide, pentaerythritol tetraacrylate isobutyramide, pentaerythritol tetraacrylate tert-butyramide, pentaerythritol tetraacrylate aminomethyl ether, pentaerythritol tetraacrylate aminoethyl ether, pentaerythritol tetraacrylate aminopropyl ether, pentaerythritol tetraacrylate aminobutyl ether, pentaerythritol tetraacrylate aminoisobutyl ether, pentaerythritol tetraacrylate aminotert-butyl ether, pentaerythritol tetraacrylate carboxymethyl ether, pentaerythritol tetraacrylate carboxyethyl ether, pentaerythritol tetraacrylate carboxypropyl ether, pentaerythritol tetraacrylate carboxybutyl ether, pentaerythritol tetraacrylate carboxyisobutyl ether, pentaerythritol tetraacrylate carboxytert-butyl ether, 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and diphenyl phosphoazide are used.

[0067] In a preferred embodiment of the present invention, the multifunctional reactive diluent is preferably selected from pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or a combination thereof.

[0068] In one embodiment of the present invention, the weight relationship between the photosensitive epoxy acrylic resin (A) (denoted as m), the black pigment enhancer (B) (denoted as n) and the reactive diluent (C) (denoted as q) containing an acrylate group and an unsaturated double bond satisfies the following relationship:

[0069] 0.50≤m / [nq / (n+q)]≤0.80;

[0070] Best

[0071] 0.60≤m / [nq / (n+q)]≤0.75;

[0072] More preferred

[0073] 0.69≤m / [nq / (n+q)]≤0.72.

[0074] In one embodiment of the present invention, the weight relationship between the photosensitive epoxy acrylic resin (A) (denoted as m), the photoinitiator (D) (denoted as p) and the reactive diluent (C) (denoted as q) containing an acrylate group and an unsaturated double bond satisfies the following relationship:

[0075] 1.20≤m / [pq / (p+q)]≤3.30;

[0076] Best

[0077] 1.49≤m / [pq / (p+q)]≤2.94;

[0078] More preferred

[0079] 1.80≤m / [pq / (p+q)]≤2.20.

[0080] In one embodiment of the present invention, the usage ratio of the photosensitive epoxy acrylic resin (A) to the black pigment enhancer (B) is 1:(2.00-3.50), preferably 1:(2.20-2.90), and more preferably 1:(2.29-2.60).

[0081] In one embodiment of the present invention, the usage ratio of the photosensitive epoxy acrylic resin (A), the active diluent (C) containing acrylate groups and unsaturated double bonds, and the photoinitiator (D) is 1: (2.50-4.50): (0.25-1.10), preferably 1: (2.99-3.84): (0.37-1.00), and more preferably 1: (2.99-3.69): (0.50-0.65).

[0082] (D) Photoinitiator

[0083] The black photoresist composition of the present invention comprises a photoinitiator. The photoinitiator is not particularly limited as long as it can absorb radiation energy, undergo chemical changes after excitation, and generate active intermediates that can initiate polymerization reactions.

[0084] In the present invention, the photoinitiator can be selected from any one of α-hydroxy ketone initiators, benzoin initiators, acylphosphine oxide initiators, acetophenone initiators, morpholinyl ketone initiators, naphthylimide photoinitiators or oxime ester photoinitiators, or a combination of at least two thereof.

[0085] In a preferred embodiment of the present invention, the photoinitiator is preferably an oxime ester photoinitiator or a combination of an oxime ester photoinitiator and other photoinitiators, such as Irgacure OEX-01, Irgacure OEX-02, Irgacure OEX-03 produced by BASF, Omnirad 1316, Omnirad 1312 produced by IGM, NCI-831, IGM-1703, IGM-1312 produced by ADEKA, which can be used alone or in combination.

[0086] (E) Additives

[0087] The black photoresist composition of the present invention contains other additives. The purpose is to ensure the stability of the performance of the composition. The additives may include surfactants, coupling agents, leveling agents, fillers, defoamers, etc.

[0088] Without affecting the efficacy of the present invention, other auxiliary agents of the black photoresist composition of the present invention are preferably silane coupling agents and leveling agents, wherein the silane coupling agent has the following general formula (I):

[0089]

[0090] In the above general formula, R is independently a methyl group or an ethyl group, and X, Y, and Z are independently an organic group such as an alkenyl group, an epoxy group, or a mercapto group.

[0091] In a preferred embodiment of the present invention, the coupling agent is selected from KBM-403, KBM-503 or KBM-903 produced by Shin-Etsu Chemical Co., Ltd.

[0092] In a preferred embodiment of the present invention, the leveling agent can be selected from BYK's BYK-371, BYK-3580 or BYK-331, preferably BYK-371.

[0093] (F) Solvent

[0094] Optional specific examples of the solvent include, but are not limited to: propylene glycol methyl ether acetate (PGMEA), cyclohexanone, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (EDM), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,4-butanediol diacetate (1,4-BDDA), 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, and one or more combinations of 2-butanone.

[0095] In a preferred embodiment of the present invention, the solvent is preferably a combination of propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ether and 1,4-butanediol diacetate.

[0096] Preparation of photosensitive resin composition

[0097] The preparation of the photosensitive resin composition of the present invention is specifically as follows: weigh a certain amount of photosensitive epoxy acrylic resin (A), black pigment enhancer (B), active diluent containing acrylate group and unsaturated double bond (C), photoinitiator (D), additive (E), solvent (F), shake at room temperature for 1.5-2.5h to mix them evenly, so as to obtain the desired photosensitive resin composition.

[0098] Preparation of black border

[0099] In addition, the present invention also provides a black matrix formed by the above-mentioned photosensitive resin composition. The above-mentioned photosensitive resin composition is sequentially coated on a glass substrate, and is prepared by pre-baking, exposure, development, and post-baking. More specifically, the black matrix of the present invention, the photosensitive resin composition used is coated on a glass substrate by spin coating, and the solvent on the glass substrate is removed by reduced pressure drying and pre-baking, and a specific pattern is formed by exposure, and the excess part is washed away by a developer, and then a post-baking treatment is performed to form a black frame.

[0100] In the preparation process of the above-mentioned black matrix, the coating speed of the photosensitive resin composition can be determined according to the specific film thickness requirements, and the film thickness is generally 1.0±0.1um. The above-mentioned reduced pressure drying can be evacuated at a pressure of 60Pa in the VCD equipment for 20s, and the pre-baking treatment is generally baked at 80℃-120℃ for 1 minute to 2 minutes. After the pre-baking treatment, exposure is carried out according to the specified center parameters, and then the temperature is developed at 23±1℃. The developer is generally potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, and other alkaline compounds. The concentration of the developer is generally 0.043%-0.055%, or other special concentrations. However, as the concentration of the developer changes, the development time needs to be adjusted accordingly.

[0101] Generally speaking, after being treated with a developer to form a specific pattern on a glass substrate, it is rinsed with water, and then excess water is blown off with an air gun, and it is air-dried and placed in an oven for post-baking treatment. The post-baking temperature is 200-240°C, and the post-baking time is 25 minutes to 40 minutes. After the above process, a specific black pattern can be formed on the glass substrate.

[0102] Preparation of spectroscopic identifier device

[0103] The preparation of the spectroscopic identifier device is similar to that of the black frame. Specifically, a black photosensitive resin composition is coated on a glass substrate, and then vacuum drying, pre-baking, exposure, development, and post-baking are performed in sequence to form circular images with different apertures. Then, different lenses, slits, and photosensitive components are added to make the device.

[0104] Preparation of automobile welcome light device

[0105] In one embodiment of the present invention, in addition to black photoresist, photoresists of other colors can also be prepared, such as photoresists showing red, green or blue, provided that the black pigment is replaced with pigments of other colors, such as red pigment, green pigment and blue pigment. In some embodiments of the present invention, the red pigment can be selected from iron oxide red (Fe2O3), cadmium red (CdS / CdSe); the green pigment is selected from chromium oxide green (Cr2O3), phthalocyanine green (PhthalocyanineGreen), cobalt green (Co2TiO4); the blue pigment can be selected from phthalocyanine blue (Phthalocyanine Blue), cobalt blue (CoAl2O4), ultramarine blue (Ultramarine Blue).

[0106] Similar to the preparation of the black frame, specifically, a black photosensitive resin composition is coated on a glass substrate, and then vacuum drying, pre-baking, exposure, development, and post-baking are performed in sequence to form circular images of different apertures, and then the carbon black is replaced with pigments of other colors (red, green, and blue), and then the prepared photosensitive resin composition (red, green, and blue) is coated on a substrate that has formed a specific black pattern, and the coating, vacuum drying, pre-baking, exposure, development, and post-baking processes are repeated in sequence to form red, green, and blue images in sequence, so as to form a colored glass sheet with a black pattern and a red, green, and blue image. Then a white light source is installed on the back to form a car welcome light with a specific color and color.

[0107] Hereinafter, the present invention will be described in detail by means of specific examples and comparative examples without limiting the scope of the present invention.

[0108] Substances used

[0109] HA Hydroxyethyl Acrylate

[0110] AIBN Azobisisobutyronitrile

[0111] PETTA Pentaerythritol Tetraacrylate

[0112] DPHA Dipentaerythritol Hexaacrylate

[0113] NCI-831 purchased from ADEKA

[0114] PGMEA Propylene glycol methyl ether acetate

[0115] EDM Diethylene glycol methyl ethyl ether

[0116] 1,4-BDDA 1,4-Butanediol diacetate

[0117] E-51 was purchased from Dow Chemical (Zhangjiagang) Co., Ltd.

[0118] WR-301 purchased from ADEKA

[0119] Example

[0120] Preparation of epoxy acrylic resin A

[0121] (1) Weigh 40 parts of hydroxyethyl acrylate (HA), 15 parts of β-hydroxypropyl methacrylate, 15 parts of isopropyl methacrylate, 50 parts of maleic anhydride (MA), 0.013 parts of p-hydroxyanisole, 0.031 parts of N,N-dimethylaniline, and 100 parts of propylene glycol methyl ether acetate, with an initial acid value of 335 mg KOH / g.

[0122] (2) Add the above reactants into a four-necked flask equipped with a stirrer, a thermometer and a dropping funnel. Make sure the equipment is clean and sealed to prevent impurities from affecting the reaction.

[0123] (3) Place the four-necked flask in an oil bath and slowly heat to 90°C while stirring to ensure that the reactants are evenly mixed. Take samples every 30 minutes to measure the acid value of the reaction solution and record the reaction progress.

[0124] (4) When the acid value is reduced to half of the initial acid value, 30 parts of epoxy resin E-51 (weight 600, epoxy functionality 2.5-6, relative density 1.22, volatile matter 0.3%) are immediately added to the reaction mixture, and the mixture is kept warm and stirred for 1.5 hours.

[0125] (5) Continue to heat the reaction mixture to 115°C and maintain this temperature to observe the change in acid value until the acid value drops to 100 mg KOH / g.

[0126] (6) Weigh 0.5 parts of azobisisobutyronitrile (AIBN), dissolve it in propylene glycol methyl ether acetate, and mix it evenly for later use.

[0127] (7) At this time, the dissolved chain initiator (azobisisobutyronitrile) is slowly added to the reaction system, and the polymerization reaction is continued under temperature control conditions to promote chain growth.

[0128] When the acid value dropped to 89 mg KOH / g, the heating was stopped and the mixture was allowed to cool naturally to room temperature, thereby obtaining a photosensitive epoxy acrylic resin having a molecular weight of 8975 g / mol and a solid content of 50%.

[0129] Preparation of epoxy acrylic resins B and C

[0130] Epoxy acrylic resins B and C were prepared according to the above method for preparing epoxy acrylic resin A, except that different amounts of raw materials were used. The performance parameters of the resins obtained are shown in Table 1.

[0131] Example 1

[0132] The preparation process is as follows: 4.02 parts of photosensitive epoxy acrylic resin A solid, 11.65 parts by weight of pigment liquid Black-SRC5 (the main component is carbon black, purchased from Mikoku Pigment Co., Ltd., with a solid content of 35.3%, of which 11.65 parts in this embodiment do not contain solvent, the solvent is propylene glycol methyl ether acetate, and the particle size is 100 nm), 4 parts of pentaerythritol tetraacrylate (PETTA), 8 parts of dipentaerythritol hexaacrylate (DPHA), 3 parts of NCI-831 photoinitiator, 3 parts of KBM-503 silane coupling agent, and 0.005 parts of BYK-371 leveling agent (solid content is 1%, in this embodiment 0.005 parts do not contain solvent) are mixed in proportion, and then 49.83 parts of propylene glycol methyl ether acetate, 15 parts of diethylene glycol methyl ethyl ether, and 1 part of 1,4-butanediol diacetate are added to obtain the corresponding photosensitive resin composition.

[0133] Example 2-11

[0134] Examples 2-9 and Example 1 use the same photosensitive epoxy acrylate resin A, except that the types and contents of the components are different, while Examples 10 and 11 use photosensitive epoxy acrylate resins B and C, respectively. Details of the contents of the components are shown in Table 1.

[0135] Comparative Examples 1-3

[0136] The resin WR-301 used in the comparative example (solid content of 50.3%, purchased from ADEKA, cardo resin, containing acrylic acid group and epoxy group cardo group) has a cardo structure, which is a common structure for resins of this type of use and has relatively stable performance. The remaining components and their contents except the resin are detailed in Table 2.

[0137] Prepare black border

[0138] The black photoresist compositions of Examples 1-11 and Comparative Examples 1-3 were respectively coated on a glass substrate by spin coating to form a coating film with a film thickness of 1.0±0.1 μm, and then the obtained coating film was vacuum dried at a pressure of 60 Pa for 20 seconds in a VCD device, and then pre-baked at a temperature of 100° C. for 2 minutes. Then, the photoresist film was patterned exposed with an exposure energy of 40 mJ and an exposure GAP of 100 μm. Next, the substrate with the exposed photoresist film was developed at a temperature of 23° C. using an aqueous solution of KOH with a concentration of 0.055% for 80 seconds.

[0139] Test Method

[0140] UV resistance test: Place the black frame substrate in the UV340 reliability equipment, set the parameters as follows: the glass surface faces the light source, 4 hours at 60℃ 0.77W, and then 4 hours at 60℃ condensation, and cycle 12 times. After the UV resistance is completed, the adhesion of the substrate is tested according to the 100-grid method of JIS.5400 (1900) 8.5.2 adhesion test.

[0141] Chemical corrosion resistance test: The black frame substrate was immersed in aqua regia at a temperature of 48° C. and a concentration of 27 v / v% for 10 minutes, and then the adhesion of the substrate was tested according to the cross-grid method of JIS.5400 (1900) 8.5.2 adhesion test.

[0142] Double 85 test: The black frame substrate was placed in a double 85 (85°C 85% humidity) reliability device for 500 hours and 1000 hours respectively. The adhesion of the substrate was then tested according to the 100-grid method of JIS.5400 (1900) 8.5.2 adhesion test.

[0143] Boiling test: The black frame substrate is immersed in boiling water for 64 hours. Then the adhesion of the substrate is tested according to the 100-grid method of JIS.5400 (1900) 8.5.2 adhesion test.

[0144] PCT test: Place the black frame substrate in a PCT (Pressure Cooker Test) device (121°C 100% humidity) and set the test time to 24 hours. Then test the adhesion of the substrate according to the 100-grid method of JIS.5400 (1900) 8.5.2 adhesion test.

[0145] Adhesion test: Use a 100-grid knife to cut 1 cut horizontally and 1 cut vertically in the black frame to form 100 small squares, then clean it with a brush, and then use 3M tape to stick to the 100-grid area, quickly pull up the 3M tape, observe the residue in the 100-grid area, and evaluate the reliability based on the following criteria:

[0146] ISO grade: 0, ASTM grade: 5B (the edges of the cut are completely smooth, and there is no peeling on the edges of the grid);

[0147] ISO grade: 1, ASTM grade: 4B (small flakes peel off at the intersection of the cuts, and the actual damage in the cross-cut area does not exceed 5%);

[0148] ISO grade: 2, ASTM grade: 3B (flaking occurs at the edges and / or intersections of the cut, with an area greater than 5% but less than 15%);

[0149] ISO grade: 3, ASTM grade: 2B (partial peeling or large peeling along the edge of the cut, or partial peeling of the grid. The peeling area exceeds 15%, but less than 35%);

[0150] ISO grade: 4, ASTM grade: 1B (exceeds the previous grade);

[0151] ISO grade: 5, ASTM grade: 0B (large pieces of the cut edge are peeled off or some squares are partially or completely peeled off, and the area is greater than 65% of the grid).

[0152] The test results of Examples 1-11 and Comparative Examples 1-3 are recorded in Table 3.

[0153] Table 1 Ratio of raw materials used in preparing photosensitive epoxy acrylic resins A, B and C and properties of the resins

[0154] Raw materials / performance Resin A Resin B Resin C Hydroxyethyl acrylate (HA) (parts by weight) 40 20 35 β-Hydroxypropyl Methacrylate (parts by weight) 15 15 25 Isopropyl methacrylate (parts by weight) 15 15 15 Maleic anhydride (MA) (parts by weight) 50 10 15 p-Hydroxyanisole (parts by weight) 0.013 2 1 N,N-Dimethylaniline (parts by weight) 0.031 1 1 Dipropyl methyl ether acetate (parts by weight) 100 30 6 Initial acid value 335 335 330 Acid value when AIBN is added Between 100-90 Between 130-120 Between 100-90 E-51 (parts by weight) 30 5 0.5 AIBN (parts by weight) 0.5 2 0.5 Number average molecular weight (g / mol) 8975g / mol 5437g / mol 13745g / mol Resin acid value (mg KOH / g) 89 114 83 Epoxy value 0.2mol / 100g 0.04mol / 100g 0.003mol / 100g The solid content of the obtained resin 33.50％ 38.7％ 31.6％

[0155] Table 2 Composition of black photoresist composition of Examples and Comparative Examples

[0156]

[0157] When calculating the amount of each component, the components do not contain solvents.

[0158] Note: A, B and C represent photosensitive epoxy acrylic resin A, B and C respectively.

[0159] Table 3 Performance evaluation

[0160]

[0161] The results of Table 3 show that, compared with the comparative example, Examples 1-11 have excellent reliability in UV resistance and chemical corrosion resistance, indicating that the addition of the photosensitive epoxy acrylic resin prepared by the present invention is helpful to improve the UV resistance and chemical corrosion resistance of the photosensitive epoxy acrylic resin composition. Among them, 5-9 are obviously better than 1-4 and 10-11. On the one hand, the amount of photosensitive epoxy acrylic resin added in Examples 1-4 is relatively small, so it can be seen that chemical corrosion resistance and double 85-1000H, PCT and other properties will improve with the increase of the amount of photosensitive epoxy acrylic resin added. On the other hand, the content of each component of the photosensitive epoxy acrylic resin composition of Example 5 is the same as that of Example 10-11, except that Examples 5, 10 and 11 use photosensitive epoxy acrylic resins A, B and C respectively, and it can be seen that the properties of the photosensitive epoxy acrylic resin, such as molecular weight, acid value and epoxy value, will also affect the chemical corrosion resistance and UV resistance of the photosensitive resin composition. Without being limited to any theory, for example, when the molecular weight of epoxy acrylic resin is small, the adhesion is good, but the cross-linking strength is poor, so the chemical corrosion resistance and UV resistance are poor. When the molecular weight is large, the adhesion is relatively poor, and the cross-linking strength is stronger, so the chemical corrosion resistance and UV resistance are relatively good. The molecular weight of epoxy acrylic resin is not the larger the better, there is a limit. Obviously, those skilled in the art can make various changes and modifications to the present application without departing from the spirit and scope of the present application. Therefore, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is also intended to include these modifications and variations.

Claims

1. A black photoresist composition comprising the following components: (A) photosensitive epoxy acrylic resin, 3.00-6.00 parts by weight, preferably 4.02-5.70 parts by weight, more preferably 5.03-5.70 parts by weight; (B) black pigment enhancer, 10-15 parts by weight, preferably 11.65-13.5 parts by weight, more preferably 12.36-13.06 parts by weight; (C) a reactive diluent containing an acrylate group and an unsaturated double bond, 10-25 parts by weight, preferably 18-21 parts by weight; (D) photoinitiator, 1-6 parts by weight, preferably 2-5 parts by weight; (E) auxiliary agent, 0.5-5 parts by weight; (F) solvent, 50-70 parts by weight, preferably 50-60 parts by weight, more preferably 53-59 parts by weight; The amounts of components (A) to (F) are based on 100 parts by weight of the total weight of the photoresist composition. The photosensitive epoxy acrylic resin has a number average molecular weight of 5000-15000 g / mol, preferably 8000-14000 g / mol, more preferably 8500-9500 g / mol, an epoxy value of 0.003-0.30 mol / 100 g, preferably 0.15-0.25 mol / 100 g, more preferably 0.18-0.22 mol / 100 g, and an acid value of 70-120 mg KOH / g, preferably 85-95 mg KOH / g.

2. The black photoresist composition according to claim 1, wherein the black pigment enhancer is selected from carbon black, titanium black, aniline black and lactam black, preferably carbon black.

3. The black photoresist composition according to claim 2, wherein the average particle size of the carbon black is 90-110 nm, preferably 95-105 nm.

4. The black photoresist composition according to any one of claims 1 to 3, wherein the reactive diluent containing an acrylate group and an unsaturated double bond is selected from pentaerythritol tetraacrylate, pentaerythritol tetraacrylate diglycidyl ether, pentaerythritol tetraacrylate dimethacrylate, pentaerythritol tetraacrylate triglycidyl ether, pentaerythritol tetraacrylate trimethacrylate, pentaerythritol tetraacrylate tetraglycidyl ether, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, tripentaerythritol tetraacrylate tri ... Pentaerythritol nonaacrylate, pentaerythritol tetraacrylate methyl ether, pentaerythritol tetraacrylate ethyl ether, pentaerythritol tetraacrylate propyl ether, pentaerythritol tetraacrylate butyl ether, pentaerythritol tetraacrylate isobutyl ether, pentaerythritol tetraacrylate tert-butyl ether, pentaerythritol tetraacrylate methyl ester, pentaerythritol tetraacrylate ethyl ester, pentaerythritol tetraacrylate propyl ester, pentaerythritol tetraacrylate butyl ester, pentaerythritol tetraacrylate isobutyl ether, pentaerythritol tetraacrylate tert-butyl ether, pentaerythritol tetraacrylate formyl Amine, pentaerythritol tetraacrylate acetamide, pentaerythritol tetraacrylate propionamide, pentaerythritol tetraacrylate butyramide, pentaerythritol tetraacrylate isobutyramide, pentaerythritol tetraacrylate tert-butyramide, pentaerythritol tetraacrylate aminomethyl ether, pentaerythritol tetraacrylate aminoethyl ether, pentaerythritol tetraacrylate aminopropyl ether, pentaerythritol tetraacrylate aminobutyl ether, pentaerythritol tetraacrylate aminoisobutyl ether, pentaerythritol tetraacrylate aminotert-butyl ether, pentaerythritol tetraacrylate carboxymethyl ether, Pentaerythritol tetraacrylate carboxyethyl ether, pentaerythritol tetraacrylate carboxypropyl ether, pentaerythritol tetraacrylate carboxybutyl ether, pentaerythritol tetraacrylate carboxyisobutyl ether, pentaerythritol tetraacrylate carboxytert-butyl ether, 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, diphenylphosphoryl azide or a combination thereof; preferably selected from pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or a combination thereof.

5. A black photoresist composition according to any one of claims 1 to 4, wherein the solvent is selected from one or more combinations of propylene glycol methyl ether acetate (PGMEA), cyclohexanone, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (EDM), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,4-butanediol diacetate (1,4-BDDA), 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, and 2-butanone; preferably, the solvent is a combination of propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ether and 1,4-butanediol diacetate.

6. The black photoresist composition according to any one of claims 1 to 5, wherein the weight relationship between the photosensitive epoxy acrylic resin (A) (denoted as m), the black pigment enhancer (B) (denoted as n) and the reactive diluent (C) (denoted as q) containing an acrylate group and an unsaturated double bond satisfies the following relationship: 0.50≤m / [nq / (n+q)]≤0.75; Best 0.65≤m / [nq / (n+q)]≤0.72; More preferred 0.69≤m / [nq / (n+q)]≤0.

72.

7. A method for preparing the black photoresist composition according to any one of claims 1 to 6, comprising the following steps: I) preparing photosensitive epoxy acrylic resin, comprising the following steps: An acrylic acid ester and an acid anhydride containing an unsaturated double bond are added into a reaction vessel as an initial mixture in a weight ratio of 5:1 to 1:1, preferably 1.7:1 to 1.1:1, wherein the initial acid value of the initial mixture is 250-350 mg KOH / g, and prepolymerization is performed, wherein the reaction temperature is 80-100° C., preferably 85-95° C., to form a prepolymer, (2) When the acid value of the prepolymer is reduced to half of the initial acid value, epoxy resin is immediately added to the prepolymer, and the reaction is carried out at the temperature in step (1) for 1-2 hours, preferably 1.3-1.7 hours. (3) raising the temperature of the reaction mixture to 100-130° C. and maintaining the elevated reaction temperature until the acid value decreases to 90-110 mg KOH / g, (4) adding a free radical polymerization initiator to continue the reaction until the acid value drops to 70-90 mg KOH / g, stopping heating, and allowing the mixture to cool naturally to room temperature, thereby obtaining a photosensitive epoxy acrylic resin. ii) the photosensitive epoxy acrylic resin obtained in step i) is mixed with a black pigment enhancer (B), a reactive diluent (C) containing an acrylate group and an unsaturated double bond, a photoinitiator (D), an auxiliary agent (E) and a solvent (F) in the proportions described in claim 1, and shaken at room temperature for 2 hours to mix them evenly to obtain a black photoresist composition.

8. A black frame, characterized in that: The invention comprises the black photoresist composition according to any one of claims 1 to 6.

9. The black frame according to claim 8, characterized in that: The invention is used for preparing touch screens, especially for preparing vehicle-mounted touch screens.

10. The black frame according to claim 8, characterized in that: The invention is used for preparing a spectroscopic identifier device and a main body material of a car welcome light device.

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